Salad oils and method of making them



United States Patent 3,353,966 SALAD OILS AND METHOD OF MAKING THEMFrederick R. Hugenberg, Deer Park, and Edwin S. Lutton, Cincinnati,Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, acorporation of Ohio No Drawing. Filed Mar. 27, 1964, Ser. No. 355,424 8Claims. (Cl. 99163) ABSTRACT OF THE DISCLOSURE Salad oil containing, asan inhibitor of solids deposition, 0.001-1% carbohydrate, 50100%esterified with -85% C14"C22 hydroxy fatty acid and 15-85% (DH-C22saturated fatty acid.

This invention relates to improved salad oils and to a method forimproving salad oils. More particularly, it relates to salad oils whichcan be stored at relatively low temperatures for extended periods oftime without clouding, and which are capable of being used in preparingmayonnaise emulsions that can be stored at low temperatures withoutbreaking of the emulsion.

Salad oils frequently are stored in refrigerators. The prolonged coolingof such oils to temperatures normally encountered in refrigerators, suchas from about 40 F. to about 50 F., generally results in the depositionof crystalline material, usually solid triglycerides, from the oil. Thismaterial may appear in the form of a cloud, or as clusters of crystals,and is considered objectionable by the consumer. In general, thetendency to form solid triglycerides in oils also adversely atfects thesuitability of the oil for use in mayonnaise emulsions. Mayonnaiseemulsions prepared from such oils tend to be unstable at lowtemperatures and are easily broken.

Frequently it is desirable to hydrogenate natural vegetable oils, suchas soybean oil, which can be used as base salad oils, in order toimprove their oxidative stability; however, hydrogenation tends toproduce oil components of decreased solubility at ordinary refrigerationtemperatures. These less soluble oil components are not completelyremoved by ordinary commercial winterization treatment, such asfractional crystallization.

Accordingly, the primary object of this invention is to provide animproved salad oil which will remain free from clouding or crystalformation for long periods of time at refrigeration temperatures. It isanother object of this invention to provide a method for retarding thedeposition of high-melting solids from salad oils.

It has now been found, according to the present invention, that thestorage time at conventional refrigeration temperatures without cloudingcan be greatly extended for a given salad oil by dissolving therein fromabout 0.001% to about 1%, by weight, of a crystallization inhibitorwhich is a carbohydrate substance esterified with both a hydroxy higherfatty acid and a saturated higher fatty acid. The carbohydrate substanceis selected from the group consisting of oligosaccharides andpolysaccharides having from 2 to about 15 saccharide units per moleculeand is about 50% to about 100% esterified, based on the total hydroxylequivalency of carbohydrate substance and higher hydroxy fatty acid.About 15% to about 85% of the esterifying carboxyl equivalency iscontributed by hydroxy fatty acid having from about 14 to about 22carbon atoms and from 1 to about 8 hydroxyl groups and about 15% toabout 85% of the esterifying carboxyl equivalency is contributed bysaturated fatty :acid having from about 14 to about 22 carbon atoms. Thebalance, if any, of the esterifying carboxyl equivalency can becontributed by fatty acid selected from the group consisting of fattyacids having from 2 to about 12-carbon atoms and unsaturated fatty acidshaving from about 14 to about 22 carbon atoms.

The oligosaccharides and polysaccharides which can be used to formsuitable esters in the practice of this invention include, by way ofillustration: disaccharides such as sucrose, maltose, lactose, andmelibiose; trisaccharides such as mannotriose and raffinose;tetrasaccharides such as stachyose; and dextrins and otheroligosaccharides and polysaccharides having up to about 15 saccharideunits per molecule.

Many of these oligosaccharides and polysaccharides are obtained fromwell-known commercial carbohydrate sources. For example, sugar canecontains about 15% to 20% sucrose and sugar beet about 10% to 17%sucrose; maltose is obtained in about yield by the enzymatic (diastase)degradation of starch; lactose is present in the milk of mammals and isa by-product of the cheese industry, produced from whey; and dextrinsare polysaccharides produced by the incomplete hydrolysis of starch withdilute acids or by heating dry starch. Sucrose is the preferredoligosaccharide for forming the carbohydrate esters of this invention.

The hydroxy fatty acids which are used to esterify the oligosaccharidesand polysaccharides are long chain, aliphatic, mono-basic hydroxy acidshaving from about 14 to about 22 carbon atoms and from '1 to about 8hydroxyl groups in the molecule. They can be, for example, the mono-,di-, tri-, and tetrahydroxy derivatives of saturated or unsaturatedfatty acids such as myristic, myristoleic, palmitic, pal-mitoleic,stearic, oleic, linoleic, linoienic, arachidic, elaidic, gadoleic,arachidonic, behenic, erucic, brassidic, and clupanodonic :acids.

Specific examples of the above hydroxy fatty acids are 9 hydroxystearic;12 hydroxystearic; 9,10 dihydroxystearic; 9, 10,'12 trihydroxystearic;9,12,13 trihydroxystearic; and 9,10,12, 13-tetrahydroxystearic acids.

All stereoisomers of the above hydroxystearic acids can be used in thepractice of this invention; for example,

erythro-9,IO-dihydroxystearic acid can be substituted forthree-9,10-dihydroxystearic acid with equivalent results.

Another common example of a specific suitable hydroxy fatty acid isricinoleic acid which is 12-hydroxy-A9-octadecenoic acid. This acid isthe major constituent of castor oil and is present in that oil as theglyceride in an amount of about 80% to Many of the desired hydroxy fattyacids can be prepared synthetically by oxidative hydroxylation ofunsaturated fatty acids through the use of oxidizing agents such aspotassium permanganate, osmium tetroxide, peracetic acid, perbenzoicacid and other peracids. For example, oleic acid can be readilydihydroxylated to form 9,10-dihydroxystearic acids and linoleic acid canbe readily tetrahydroxylated to form 9,10,12,13-tetrahydroxystearicacids by methods well known to those skilled in the art. Trihydroxyfatty acidscan be readily obtained from castor oil by reaction withperacetic acid followed by saponification and splitting off of thedesired acids in accordance with well-known methods of preparation.

The saturated higher fatty acids which are used to esterify theoligosaccharides and polysaccharides are long chain aliphatic monobasicacids having from about 14 to about 22 carbon atoms and includemyristic, palmitic, stearic, arachidic, and behenic acids. These fattyacids can be readily obtained from hydrogenated glycerides bysaponification, acidulation, and isolation procedures. The fatty aciddesired determines the choice of glyceridic material used. For example,a technical grade of stearic acid can be obtained from highlyhydrogenated soybean oil and a technical grade of behenic acid can beobtained from highly hydrogenated rapeseed oil.

By way of example, a suitable ester for this invention is sucroseesterified with an average of 2 hydroxy higher fatty acid groups and 4palmitic acid groups. Other long chain saturated fatty acid groups suchas myristic, stearic, arachidic, and behenic acids, and mixturesthereof, can be present in place of part or all of the palmitic acidgroups. The oligosaccharides and polysaccharides should be at leastabout 50% esterified, based on the total hydroxyl equivalency ofoligosaccharides and polysaccharides and hydroxy higher fatty acid,about 15% to about 85% of the total esterifying carboxyl equivalencybeing applied by hydroxy higher fatty acid and about 15% to about 85% ofthe total esterifying carboxyl equivalency being supplied by saturatedmonobasic higher fatty acid. Subject to this limitation, carboxylequivalency can be supplied additionally from short chain fatty acidssuch as acetic, propionic, butyric, valeric and caproic acids, or fromlong chain unsaturated fatty acids such as myristoleic, palmitoleic,linoleic, linolenic, elaidic, gadoleic, arachidonic, erucic, brassidic,and/ or clupanodonic acids.

The oligosaccharide and polysaccharide esters of this invention can beprepared by various well-known methods for preparing esters. Forexample, the oligosaccharides and polysaccharides can be reacted withacid anhydrides of suitable hydroxy fatty acids and saturated fattyacids or of (hydroxy-esterified) hydroxy fatty acids.

It is preferred to obtain the oligosaccharide and polysaccharide estersby means of alcoholysis with the methyl esters of the hydroxy higherfatty acids and saturated higher fatty acids in the presence of suitablecatalysts. In these interesterification reactions, it is preferable toreact the oligosaccharides and polysaccharides with a methyl ester ofthe hydroxy higher fatty acid followed by reaction with a methyl esterof the saturated higher fatty acid, although the reverse order ofinteresterification can be used if desired. Mutual solvents such asdimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane,pyridine, xylene and toluene are of good value in theseinteresterification reactions. Catalysts of greatest value are suchcompounds as sodium methoxide, benzyl trimethyl ammonium methoxide, andothers described by Eckey, US. Patent 2,442,532, at col. 24, line 18 etseq., granted June 1, 1948.

Since the hydroxyl groups on the hydroxy fatty acid are esterifiable aswell as those on the oligosaccharides and polysaccharides, it should beunderstood that branching of the acid chain can occur during the aboveesteri fication or interesterification reactions. This chain-branching,of course, would tend to occur more extensively when the polyhydroxyacids are used. In actual practice, partial removal of branched methylesters and acids from the reaction products was facilitated by acombination of distillation and alcohol washing or extraction, but itshould be understood that the esterified oligosaccharide crystallizationinhibitor of this invention can include ester mixtures which contain thebranched acid chains.

Although various methods of preparation of the crystallizationinhibitors of this invention are described herein, it is to beunderstood that the invention is not to be limited to any specificmethod of preparation of these compounds.

A wide variety of oils can be used as base oils which can be maderesistant to deposition of high-melting solids at low temperatures inaccordance with this invention. Included among suitable oils are theso-called natural salad oils such as olive oil, sunflower seed oil,safliower oil and sesame seed oil. Oils such as cottonseed oil and cornoil preferably are given a preliminary Winterizing, dewaxing, or similarother treatment to remove the highermelting solids to form a good basesalad oil. Other oils, such as soybean oil, may require hydrogenation toimprove resistance to oxidative deterioration with prolonged storage,and the higher-melting glycerides formed during this hydrogenationtreatment preferably are removed by winterization. Base salad oils canbe formed also by directed, low-temperature interesterification ofanimal or vegetable fatty material, followed by removal of highermeltingglycerides formed du g U16 r a tio 5 for example, U.S. Patent 2,442,532,granted to E. W. Eckey, June 1, 1948. Another group of oils includesthose in which one or more short chain or lower fatty acids having from2 to about 6 carbon atoms, such as acetic and propionic acids, replace,in part, the longer chain or higher fatty acids present in naturaltriglyceride oils. Other base salad oils will suggest themselves tothose skilled in the art, provided they have a suitable chill test ashereinafter defined. The base salad oils can be used individually or asmixtures of oils. As used herein, the term base salad oil is intended toinclude any salad oil which will not immediately form solids when cooledto 30 F.

The procedure for measuring the resistance of salad oils to clouding andthe crystal inhibiting activity of the esters as used hereinafterinvolves preheating the oil or oil with inhibitor to a temperature ofabout 140 F., then aircooling a 100 gram sample at about 30 F. untilsolids form in the oil. As used herein, the term chill test is intendedto define the total length of time at 30 F. (unless some othertemperature is specified), until such solids form.

The ester and the base salad oil can be mixed together in any convenientmanner. For example, ester in liquid form can be mixed with the oil. Ifthe ester is in solid form, it can be dissolved in the oil, although itmay be desirable to heat the oil or the mixture of the oil and ester tofacilitate solution. It is to be kept in mind, however, that in allcases the resulting product is merely a physical mixture and there is nochemical reaction between the ester and the oil.

The following examples which come within the scope of the claims willserve to further illustrate the invention; however, it should beunderstood that the invention is not limited to these illustrativeexamples since the skilled artisan will be able to devise many moreexamples after reading the specification and appended claims. In each ofthe esterified carbohydrate substances used as crystallizationinhibitors in these examples, the carbohydrate substance is from about50% to about 100% esterified, based on the total hydroxyl equivalency ofcarbohydrate substance and esterifying hydroxy fatty acid, from about 15to about of the esterifying carboxyl equivalency being contributed bymaterial selected from the group con sisting of saturated andunsaturated hydroxy fatty acids having from about 14 to about 22 carbonatoms and from 1 to about 8 hydroxyl groups, from about 15 to about 85%of the esterifying carboxyl equivalency being contributed by saturatedfatty acids having from about 14 to about 22 carbon atoms, and anybalance of the esterifying carboxyl equivalency being contributed bymaterial selected from the group consisting of fatty acids having from 2to about 12 carbon atoms and unsaturated fatty acids having from about14 to about 22 carbon atoms.

Example 1 Methyl ester of hydrogenated castor oil was prepared byrefluxing hydrogenated castor oil with methanol in the presence ofalkaline catalyst as follows:

One kilogram of hydrogenated castor oil (iodine value 3.51; acid value2.58; saponification value 178.5; and hydroxyl value 157.0) was warmedin 400 grams methanol. Three grams KOH dissolved in grams methanol wasadded and the mixture was refluxed for 2 hours on a steam bath. Oneliter of hexane was added to the mixture, and it was allowed to stand atroom temperature for about 12 hours. Then 250 grams of water was addedand the product was thoroughly washed and recovered. Flash distillationyielded 819 grams of methyl ester product having the following analysis:

Iodine value 2.35 Acid value 2.41 Saponificat'ion value 182.2 Hydroxylvalue 145.7

Mixed sucrose ester of hydrogenated castor oil and palmitic acid wasprepared by catalytic alcoholysis of sucrose and the above methyl esterfollowed by acylation with palmitoyl chloride as follows:

Sucrose (11.4 grams) was reacted with methyl ester of hydrogenatedcastor oil (100 grams) in the presence of dimethylformam-ide (100 cubiccentimeters) and Triton B40% benzyl trimethylammonium hydroxide catalystin methanol(10 cubic centimeters) at 60 to 70 C. The methyl alcoholformed by the reaction was driven off by heating with 100 cubiccentimeters cyclohexane at 120 to 135 C. over a 3-hour period. Thesolvents, dimethylformamide and cyclohexane, were stripped off and thereaction product was held under high vacuum for 2 hours at 140 to 145 C.The product (97 grams) was water-washed and recovered from hexane.Analysis:

Twenty grams of the above product was treated with twenty gramspalmitoyl chloride in 10 cubic centimeters pyridine and 100 cubiccentimeters toluene. The ester was first dissolved in the solvents andthen the fatty acid chloride was slowly added with cooling in a waterbath. After standing for 2 hours, the reaction mixture was heated toreflux temperature and then allowed to stand at room temperature for 2days. The solvents were stripped off and the product (30 grams) waswashed with water, then washed with .5 K CO solution and was thenrecovered from hexane. Analysis:

Acid value 10.9 Saponification value 196.7 Hydroxyl value Total fattyacid percent 98.8

When the above mixed sucrose ester of hydrogenated castor oil acids andpalmitic acid was dissolved in salad oil consisting of 90% winterizedcottonseed oil (refined and bleached liquid oil) and 10% cottonseed oil(refined and bleached liquid oil) and held at 30 F., the chill test wasextended beyond the 12 hours for the original salad oil withoutinhibitor as follows:

Percent added ester: Chill test, hours 0.0 12

Example I] Sucrose (6.85 grams) was dissolved in dimethylformamide (100cubic centimeters) at 80 C. Then 58 grams of the methyl ester ofhydrogenated castor oil prepared as in Example I and cubic centimetersof Triton B was added. After 30 minutes, the mixture was placed underhigh vacuum at 100 C. and the temperature was increased very slowly to150 to 160- C. during a period of about 2 hours whereby the solvent wasdistilled off. The sucrose ester product was water-Washed and recovered,and then the excess methyl esters were topped out of the product at 190to 210 C. -by distillation.

Five grams of the above sucrose ester product was further esterified byreaction with ten grams palmitoyl chloride in the presence of cubiccentimeters pyridine and 50 cubic centimeters toluene. The reactionmixture Acid value 27.5 Saponification value 204.9 Hydroxyl value 0Total fatty .acid percent 95.6

When the above mixed sucrose ester of hydrogenated castor oil acids andpalmitic acid was dissolved in the salad oil of Example I and held at 30F., the chill test was extended beyond the 12 hours for the originalsalad oil without inhibitor as follows:

Percent added ester: Chill test, hours Example III A mixed sucrose esterwas prepared from Sucrodet (a commercial sucrose dipalmitate-acid value1.5; Saponification value 115.6; hydroxyl value 426; total fatty acid58.8%) by methanolysis with the methyl ester of the hydrogenated castoroil of Example I as follows:

Sucrodet (32.7 grams) was reacted with the hydrogenated castor oilmethyl esters (82.1 grams) in the presence of cubic centimetersdimethylformamide, 100 cubic centimeters cyclohexane and 5 cubiccentimeters Triton B at 90 to C. for 3 to 4 hours. The solvents werestripped off under high vacuum at to C. and the product was water-washedand recovered from hexane. Excess methyl ester was then topped out ofthe product by distillation at 205 C. and 95 grams of purified productwas recovered. Analysis:

Acid value 3.6 Saponification value 164.6 Hydroxyl value 86.1 Totalfatty acid percent 91.5

When the above mixed sucrose ester of hydrogenated castor oil acids .andpalmitic acid was dissolved in the salad oil of Example I and held at 30F., thechill test was extended beyond the 12 hours for the originalsalad oil without inhibitor as follows:

Percent added ester: Chill test, hours When equivalent weights ofsucrosedipalmitate monoacetate or sucrose dipalmitate monooleate aresubstituted for sucrose dipalmitate in the preparation and use of themixed sucrose ester in the above example, substantially similarimprovements in chill test results are obtained.

Example IV Fifty grams of the mixed palmitic and hydrogenated castor oilacid sucrose ester of Example III was further acylated with thirty-sevengrams palmitoyl chloride in the presence of pyridine and toluene toyield eighty-four grams of esterified product. Analysis:

Acid value 5.3 Saponification value 190.4 Hydroxyl value 31.1 Totalfatty acid percent 83.8

When the above mixed sucrose ester of hydrogenated castor oil acids andpalmitic acid was dissolved in the salad oil of Example I and held at 30F., the chill test was extended beyond the 12 hours for the originalsalad oil without inhibitor as follows:

Percent added ester: Chill test 0.0 hours 12 0.1 do 198 0.3 days 31 Thechill tests described in Examples V to XIII, below, employed the sameprocedure and base salad oil described in Example I.

Example V (a) Sucrose (34 grams) was reacted with methyl ester ofhydrogenated castor oil (135 grams) in the presence ofdimethylformamide, cyclohexane, .and Triton B at 125 to 130 C. for 2hours. After solvent-stripping, water-washing, and recovery from ethylacetate, the product showed the following analysis:

Acid value 2.7 Saponification value 138.3 Hydroxyl value 192.9 Totalfatty acid "percent" 97.0

Acid value 7.6 Saponification value 174.1 Hydroxyl value 7.8 Total fattyacid percent 95.1

Percent added ester: Chill test, hours 0.0 12 0.1 200 0.3 (slight haze)375 Example Vl Example V(b) was repeated except that 45 grams of thesucrose ester of Example V(a) was reacted with 83 grams of stearoylchloride instead of with palmitoyl chlo ride. An ester product (121grams) was recovered with the following analysis and chill test:

Acid value 0.4 Saponification value 182.8 Hydroxyl value 23.1 Totalfatty acid percent 95.5

Percent added ester: Chill test, hours 0.0 12

0.1 150 0.3 (slight haze) 150 Example VII The ethanol insoluble fraction(at room temperature) of the product of Example VI yielded the followinganalysis and chill test:

Acid value 5.3 Saponification value 173.4 Hydroxyl value 9.8 Total fattyacid percent 96.4 Percent added ester: Chill test, hours Example VIIISucrose (17.1 grams) was reacted with methyl palrnitate (81 grams) in200 cubic centimeters dimethylformamide and cubic centimeters Triton Bat 100 C. for /2 hour. Then 200 cubic centimeters of cyclohexane was 8added and the methyl alcohol Was azeotropically distilled out of themixture over a 3-hour period. Thirtyfive grams of the methyl ester ofhydrogenated casto oil of Example I was added to the reaction mixtureand agitated at C. for 2 hours. Five cubic centimeters Triton B was thenadded. After heating the mixture at to C., 200 cubic centimeterscyclohexane was added. The solvents were stripped off under high vacuumat 135 C. for about 2 hours, whereby 59 grams of product was recovered.Fifty grams of the product was reacted with 15 grams of palmitoylchloride in 200 cubic centimeters cyclohexane and 10 cubic centimeterspyridine. The mixture was agitated and allowed to stand at roomtemperature for 2 days. An ester product (65 grams) was recovered withthe following analysis and chill test:

Acid value 4.6 Saponification value 186.2 Hydroxyl value 93.2 Totalfatty acid percent 87.8

Percent added ester: Chill test, hours 0.0 12 0.1 30 0.3 30

Example IX Fifty-six grams of the mixed sucrose ester of Example VIIIwas reacted with 15 grams of palmitoyl chloride in 100 cubic centimeterscyclohexane and 10 cubic centimeters pyridine. The reaction mixture wasallowed to stand at room temperature for 2 days. An ester product (66grams) was recovered from hexane. Analysis and chill test:

Acid value 0.3 Saponification value 186.0 Hydroxyl value 11.0 Totalfatty acid percent 90.4

Percent added ester: Chill test, hours Example X A methyl ester of12-hydroxystearic acid was prepared by reacting 40 grams of12-hydroxystearic acid (acid value 185.5; melting point 79 to 81 C.)with 200 grams methanol, the reaction being catalyzed with sulfuricacid. The reaction mixture was refluxed one hour and then allowed tostand at room temperature for 12 hours. The product was water-washed andthen recovered from hexane (41.5 grams). Analysis:

Acid value 2.0 Saponification value 178.0 Hydroxyl value 106.0

A sucrose ester was prepared by reacting 3.42 grams sucrose with 19.5grams of the above methyl ester of 12-hydroxystearic acid in 25 cubiccentimeters cyclohexane, and 2.5 cubic centimeters Triton B at about C.Ten grams of the sucrose ester product was then acylated with 13 gramspalmitoyl chloride in the presence of cyclohexane and pyridine to yield19 grams of the mixed sucrose ester. Analysis and chill test:

Acid value 0.9

Saponification value 181.0

Hydroxyl value 2.0

Total fatty acid percent- 96.6

Percent added ester: Chill test, hours 0.0 12 01 0 3 250 9 Example XITrihydroxy acids were prepared after the method of Kass and Radlove, 64J. Amer. Chem. Soc. 2253 (1942), by action of peracetic acid on castoroil followed by saponification and splitting. The trihydroxy acids werethen crystallized from ethyl acetate.

Eighty-five grams of the above-formed trihydroxy acid was refluxed with162 grams methanol and 2 grams sulfuric acid to form methyl ester. Thismethyl ester was used to form two surcro'se ester reparations asfollows:

(a) Sucrose (8.5 grams) reacted with methyl ester (50 grams) in 50 cubiccentimeters dimethylformamide and 50 cubic centimeters cyclohexaue and10 cubic centimeters Triton B at 125 C.

(b) Sucrose (5.13 .grams) reacted with methyl ester 15.6 grams) in 50cubic centimeters dimethylformamide, 50 cubic centimeters cyclohexaneand 10 cubic centimeters Triton B at 125 C.

Reaction products from (a) and (b) were then separately acylated withpalmitoyl chloride in the following proportions to form mixed sucroseesters:

Twenty grams of (a) reacted with 80 grams palmitoyl chloride in 50 cubiccentimeters cyclohexane and 50 cubic centimeters pyridine, yielded aproduct of the following analysis and chill test:

Forty-five grams of (b) reacted With 5 0 grams palmitoyl chloride in 50cubic centimeters cyclohexane and 50 cubic centimeters pyridine, yieldeda product of the following analysis and chill test:

Acid value 0.7 Saponification value 206.0 Hydroxyl value 2.0 Total fattyacid per nt 99.2

Percent added ester: Chill test, hours Example XII Tetrahydroxy acidswere prepared from linoleic acid by using the method of Hazura, 29Biochem. J. 1554 (1935) according to which the potassium soap oflinoleic acid was treated with potassium permanganate followed bytreatment with S0 and HCl. The tetrahydroxy acids were then crystallizedfrom ethyl acetate.

The tetrahydroxy acid (1100 grams) was refluxed with methanol (450 cubiccentimeters) and sulfuric acid (2 cubic centimeters) to form the methylester thereof. A sucrose ester of the tetrahydroxy acid was prepared byreacting 3.42 grams of sucrose with 20 grams of the above methyl ester;and a mixed sucrose ester was prepared by reacting 8 grams of the methylester product with 50 grams palmitoyl chloride, both reactions beingcarried out in the manner described for the trihydroxy esters of ExampleXI. Analysis and chill test:

10 Example XIII A methyl ester of dihydroxystearic acid was prepared byrefluxing 118 grams of 9, 10-dihydroxystearic acid (melting point to 92C.; obtained by crystallization of 9,10 cis acids) with 375 cubiccentimeters methanol and 2 grams sulfuric acid for 2 hours. A sucroseester was prepared from this methyl ester by reacting 3.42 grams ofsucrose with 18.2 grams of the methyl ester in dimethylformamide andcyclohexane in accordance with the procedure in Example XI for preparingthe trihydroxy esters. The sucrose ester was acylated to form a mixedsucrose ester by reacting 10 grams of the ester with 24 grams ofpolymitoyl chloride in dimethylformamide and cyclohexane in substantialaccordance with the acylation procedure described in Example XI. Thealcohol insoluble portion of the reaction product had the followinganalysis and chill test:

When an equivalent weight of behenoyl chloride is substituted for thepalmitoyl and stearoyl chlorides in the above examples, substantiallyequivalent chill test results are obtained.

If too large an amount of inhibitor is present in the salad oil, it willbe precipitated out of the oil as the oilinhibitor mixture is cooled,and possibly even promote crystallization of high-melting solids in theoil. Too small an amount of inhibitor, of course, will be relativelyineffective. Amounts of ester in excess of 1%, by weight, areunnecessary as affording no significant added improvement of the oil;and it is preferred to use from about 0.05% to about 0.1%. A salad oilhaving dissolved therein about 0.1% sucrose fully esterified withhydroxy fatty acid and palmitic acid in a ratio of about 1:1 is a verydesirable example of the invention herein defined.

What is claimed is:

1. A clear glyceride salad oil having improved resistance to depositionof high-melting solids and compirsing a base salad oil having dissolvedtherein from about 0.001% to about 1%, by weight, of esterifiedcarbohydrate substance selected from the group consisting ofoligosaccharides and polysaccharides having from 2 to about 15saccharide units per molecule, said carbohydrate substance being fromabout 50% to about esterified, based on the total hydroxyl equivalencyof carbohydrate substance and esterifying hydroxy fatty acid, from about15% to about 85 of the esterifying carboxyl equivalency beingcontributed by material selected from the group consisting of saturatedand unsaturated hydroxy fatty acids having from about 14 to about 22carbon atoms and from 1 to about 8 hydroxyl groups, from about 15 toabout 85% of the esterifying carboxyl equivalency being contributed bysaturated fatty acids having from about 14 to about 22 carbon atoms, andany balance of the esterifying carboxyl equivalency being contributed bymaterial selected from the group consisting of fatty acids having from 2to about 12 carbon atoms and unsaturated fatty acids having from about14 to about 22 carbon atoms.

2. The clear glyceride salad oil of claim 1 in which the carbohydratesubstance is sucrose.

3. The clear glyceride salad oil of claim 1 in which the esterifyingsaturated fatty acid is palmitic.

4. The clear glyceride salad oil of claim 1 in which the esterifyinghydroxy fatty acid is derived from hydrogenated castor oil.

5. The clear glyceride salad oil of claim 1 in which the base salad oilis derived from cottonseed oil.

1 1 1 2 6. Theclear glyceride salad oil of claim 1 in which theReferences Cited base salad oil is derived from hydro enated soybeanoil. UNITED STATES PATENTS 7. The clear glyceride salad oil of ilairn 1in which the 6 esterified carbohydrate substance is present in an amount2 3 2 Eckey et a1 99 of from about 0.05% to about 0.1% by weight. 5 9[11/19 Baur et a1 99118 8. A clear glyceride salad oil comprising a basesalad $158,490 11/1964 Baur et a1 99 118 oil having dissolved thereinabout 0.1% sucrose fully esterified with hydroxy fatty acid andpalrnitic acid in a LOUIS MONACELL P'lmary Examine" ratio of about 1:1.MAURICE W. GREENSTEIN, Examiner.

1. A CLEAR GLYCERIDE SALAD OIL HAVING IMPROVED RESISTANCE TO DEPOSITIONOF HIGH-MELTING SOLIDS AND COMPRISING A BASE SALAD OIL HAVING DISSOLVEDTHEREIN FROM ABOUT 0.001% TO ABOUT 1%, BY WEIGHT, OF ESTERIFIEDCARBOHYDRATE SUBSTANCE SELECTED FROM THE GROUP CONSISTING OFOLIGOSACCHARIDES AND POLYSACCHARIDES HAVING FRO M 2 TO ABOUT 15SACCHARIDE UNITS PER MOLECULE, SAID CARBOHYDRATE SUBSTANCE BEING FROMABOUT 50% TO ABOUT 100% ESTERIFIED, BASED ON THE TOTAL HYDROXYLEQUIVALENCY OF CARBOHYDRATE SUBSTANCE AND ESTERIFYING HYDROXY FATTYACID, FROM ABOUT 15% TO ABOUT 85% OF THE ESTERIFYING CARBOXYLEQUIVALENCY BEING CONTRIBUTED BY MATERIAL SELECTED FROM THE GROUPCONSISTING OF SATURATED AND UNSATURATED HYDROXY FATTY ACIDS HAVING FROMABOUT 14 TO ABOUT 22 CARBON ATOMS AND FROM 1 TO ABOUT 8 HYDROXYL GROUPS,FROM ABOUT 15% TO ABOUT 85% OF THE ESTERIFYING CARBOXYL EQUIVALENCYBEING CONTRIBUTED BY SATURATED FATTY ACIDS HAVING FROM ABOUT 14 TO ABOUT22 CARBON ATOMS, AND ANY BALANCE OF THE ESTERIFYING CARBOXYL EQUIVALENCYBEING CONTRIBUTED BY MATERIAL SELECTED FROM THE GROUP CONSISTING OFFATTY ACIDS HAVING FROM 2 TO ABOUT 12 CARBON ATOMS AND UNSATURATED FATTYACIDS HAVING FROM ABOUT 14 TO ABOUT 22 CARBON ATOMS.